Ibuprofen complexes as wood preservatives

ABSTRACT

Complexes of ibuprofen and copper and/or zinc were solubilized in ammoniacal solution providing preservative solutions that fully penetrate wood. With loss of the ammonia from the wood, the complexes were stably retained in the wood providing a long lasting preservative.

This application claims the benefit of U.S. Provisional Application No.60/755,214, which is incorporated in its entirety as a part hereof forall purposes.

TECHNICAL FIELD

This invention relates to preservatives for wood and other cellulosicmaterials. Specifically, protection of cellulosic materials is providedby the application of solutions of ibuprofen complexed with copper orzinc ions. These complexes readily penetrate the cellulosic materials.

BACKGROUND

The decay of wood and other cellulosic materials by fungi, and theconsumption of wood by termites, cause significant economic loss. Untilrecently, the most widely used wood preservative has been chromatedcopper arsenate (CCA). However, production of CCA for use in residentialstructures was prohibited as of January 2004 due to issues raisedconcerning the environmental impact and safety of arsenic and chromiumused in CCA-treated lumber. As CCA replacements, arsenic-free andchromium-free wood preservatives are sought. Retention in treated woodof copper and other metal ions that are effective fungicides is achallenge. Metal salts are generally water soluble and rapidly leachfrom treated wood, which causes loss of the preservative function.

Wood rotting fungi are typically either white-rot or brown-rotbasidiomycetes. Brown-rot fungi are the most destructive wood rottingorganisms, though they make up only 7% of all wood rottingbasidiomycetes (Gilbertson and Ryvarden (1986) North American Polypores,Abortiporus-Lindtneria, Vl. Gronslands Grafiske A/S, Olso, Norway). Thebrown-rot fungi are generally tolerant of copper, the typically usedwood preservative, which is effective against the white-rot fungi. Thus,compounds active against brown-rot fungi are needed in woodpreservatives.

Ibuprofen has been shown to be toxic to many different isolates ofbrown-rot fungi [Clausen, Report #IRG/WP 10160, (1996) USDA ForestProducts Lab., Madison, Wis.]. In addition, ibuprofen has been found tobe toxic to termites (Connick et al, (2001) Environmental Entomology, v30, p 449-455). The potential value of ibuprofen as a wood preservative,however, would be limited by the fact that is only slightly soluble inwater, so solutions with effective wood preservative concentrationscannot be readily made.

Thus there is a need for ibuprofen-containing wood preservatives thatcan penetrate wood, and yet be fixed in the wood to provide long-termprotection.

SUMMARY

One embodiment of this invention provides an aqueous compositioncomprising in admixture (a) a complex comprising (i) ibuprofen, and (ii)copper ions, zinc ions or a mixture thereof; and (b) ammonia and/orethanolamine; wherein component (b) is present in an amount sufficientto solubilize the complex.

Another embodiment of this invention provides a process for preparing acomposition by combining the components (a) and (b) described above, andsolubilizing a complex as formed therefrom.

A further embodiment of this invention provides a process for preservinga cellulosic material, or an article that comprises a cellulosicmaterial, comprising contacting the cellulosic material or the articlewith the composition described above.

Yet another embodiment of this invention provides a cellulosic material,or an article comprising a cellulosic material, wherein the abovedescribed composition is adsorbed on or absorbed in the cellulosicmaterial.

DETAILED DESCRIPTION

A complex that is formed from ibuprofen, and copper and/or zinc ions, issolubilized by, for example, ammonia or ethanol amine, and is used insuch form as a deeply-penetrating and long lasting preservative for woodand other cellulosic materials. As the metal ion complex is solubilizedin an aqueous medium, it can be readily adsorbed onto, and/or absorbedor imbibed into, wood or other cellulosic materials. Upon loss orevaporation of the solvent or co-solvents in the solution, the complexbecomes insoluble, thereby fixing the ibuprofen and the metal ion(s)within the target material, and providing an effective preservativecomposition for the cellulosic material.

A cellulosic material is preserved in the sense that contact with acomposition of this invention protects the material against decay ordeterioration from deleterious effects as caused by either or both ofpests and living organisms. Resistance to brown-rot fungi is imparted tothe cellulosic materials due to the brown-rot fungicidal activity ofibuprofen, and white-rot fungal protection is imparted due to the copperand/or zinc ions. The termiticidal activity of ibuprofen also aids inpreservation of the cellulosic materials. The potential fordeterioration or destruction of a cellulosic material by exposure tonatural conditions or hazards is thus reduced and preferably preventedby the presence in and/or on the material of a composition of thisinvention. A process of this invention provides preservation forcellulosic materials by providing contact of the materials with acomposition of this invention, and thus achieves the benefits ofprotection against adverse conditions, pests and organisms, such astermites and fungi as described above.

The cellulosic materials that can be treated with a composition of thisinvention are those that contain or are derived from cellulose, which isa polysaccharide that forms the main constituent of the cell wall inmost plants, and is thus the chief constituent of most plant tissues andfibers. These cellulosic materials include wood and wood products suchas lumber, plywood, oriented strand board and paper, in addition tolignin, cotton, hemicellulose and cellulose itself. References herein tothe preservation of wood by the use of a composition of this invention,or by the performance of a process of this invention, or references tothe usefulness of a composition hereof as a wood preservative, shouldtherefore be understood to be references to the preservation of alltypes of cellulosic materials, not just wood alone.

Ibuprofen with Copper/Zinc in Solution

Ibuprofen used to prepare preservative solutions of this invention maybe supplied as ibuprofen or sodium ibuprofenate. These compounds aresoluble in methanol and ethanol but relatively insoluble in water.

The fungitoxic metals copper and zinc, in ionic state, e.g. copper ion,may be used to form complexes with ibuprofen that are solubilized inorder to provide a preservative composition according to this invention.Any soluble copper salt may be a source of copper ions, for example,Cu(II) salts may include copper sulfate, copper sulfate pentahydrate,cupric chloride, cupric acetate, and copper carbonate. Particularlyuseful as the copper salt is copper sulfate pentahydrate. Any solublezinc salt may be a source of zinc ions, for example Zn(II) salts mayinclude zinc sulfate, zinc chloride, zinc acetate, zinc nitrate, andzinc carbonate. Particularly useful as the zinc salt is zinc acetate.Mixtures of copper ion sources and zinc ion sources may be used in thecompositions of this invention as well. Sources of ibuprofen, and copperions and zinc ions, as described above, are available commercially.

To form a composition of this invention, the components thereof arecombined in admixture. For example, an aqueous solution may be preparedthat contains ibuprofen or an ibuprofen salt, and a copper and/or zincsalt or other source of copper ions. The mixture in solution of thecomponents as described above forms a complex. A complex as used hereinis essentially a salt, but may also be described as an associationcontaining organic and/or inorganic components in any combination thatis held together by covalent or electrostatic bonds, or by bonds thatare intermediate between covalent and electrostatic bonds such as in acoordination compound. One example of the combination of components asmentioned above leads to formation of a complex between an ibuprofenateand a copper ion, and the complex precipitates in aqueous solution, asshown in Diagram I. Shown is a simplified diagram. The structure of thecopper complex can be found in Trinchero et al, Biopolymers (2004) 74, p120-124.

By combining these components in an aqueous ammoniacal solution, theibuprofenate and metal ion complex was found to remain fully soluble asshown in Diagram II:

In preparing this solution, it is particularly useful to includeammonium hydroxide in sufficient concentration to preclude the formationof a precipitate while mixing the components. A solvent or co-solventsuch as ammonia is present in sufficient amount to maintain solubilityof the complex in the aqueous mixture. Typically, ammonia as used toprepare the solution is used in an amount such that it is present atabout 0.5% to 3% by weight in the final solution. Preferred is 1.4 wt %ammoniacal water solution. Ethanolamine may be used in an amount ofabout 0.5% to 3% by weight of the solution as an alternative to ammonia.Additionally, combinations of ethanolamine and ammonia may be used.Although use of ammonia is preferred, other solvents or co-solvents thatform a solution with water, that solubilize the complex as readily asammonia, and also evaporate as readily as ammonia from the cellulosicmaterial after treatment, may also be used in addition to or in place ofammonia or ethanol amine in the solvent system in which the complex issolubilized.

In general, solubility of the complex is determined by visualobservation, and a complex is considered to be solbilized when asufficient amount of the complex is dissolved in the solution to permita desired amount of the complex to be adsorbed on and/or absorbed in thecellulosic material when the treatment thereof occurs.

Mixtures of ibuprofen with copper and/or zinc ions are used in thepreservative compositions of this invention in amounts effective toprovide a desired level of protection in view of the service conditions(including the nature of the target material, the contemplated end use,and the geographic location) that the cellulosic material to be treatedwill experience. The concentration of ibuprofen in the treatmentsolution is thus usually in the range of about 100 to about 20,000 ppm,or in the range of between about 100 to about 1,000 ppm, or in the rangeof between about 200 to about 700 ppm, or in the range of about 300 toabout 500 ppm. The copper and/or zinc ions are typically used at aconcentration in the treatment solution in the range of about 500 ppm toabout 11,000 ppm. Marine use generally requires the higherconcentrations, up to about 11,000 ppm while land use may involveconcentrations between about 500 and 6,000 ppm. It is particularlyuseful to include corresponding amounts of ibuprofen and copper and/orzinc such that these components are present in a complex in comparableamounts. One method of determining the content of a complex in a treatedcellulosic material is to burn the material and analyze the ash for itscontent of the components that have been used to prepare the complex. Acomposition hereof may be made by mixing the components in any suitabledevice, such as a blender or rotating mixer.

Though the preservative compositions of this invention that are used intreating cellulosic materials are largely if not completely dissolved insolutions such as ammoniacal solutions, a more concentrated master batchmay be made that is readily transported for commercial purposes, andthen diluted prior to use. Such a concentrated master batch may be aslurry, containing partially precipitated ibuprofen-copper and/or zinccomplexes. The slurry is prepared for use in treatment by increasing thevolume of solution by the addition of one or more solvents orco-solvents, for example to a final concentration where ammonia is usedin the solvent system and an approximately 1.4 wt % ammoniacal watersolution is obtained.

Features of Ibuprofen and Copper and/or Zinc Complexes in AmmoniacalSolution as Wood Preservative Compositions

The solubility properties of the ibuprofen and copper and/or zinccomplexes as used herein provide specific attributes valuable in apreservative composition. These complexes are insoluble in water, buthave been found to typically be well dissolved, if not be completelysoluble, in a solvent system such as an ammoniacal solution. When thecomplex is well dissolved in the solvent system, deep penetration of thepreservative solution into cellulosic material such as wood, well pastthe surface wood, is obtained. Following penetration, a solvent orco-solvent such as ammonia readily evaporates from the wood, leaving thebrown-rot fungicidal and termiticidal ibuprofen and the white-rotfungicidal copper and/or zinc ions as a complex in the wood where itbecomes precipitated and binds tenaciously to cellulose. Thus, there islittle leaching of ibuprofen or copper and/or zinc ions from the treatedwood.

Additional Components in Wood Preservative Solution

Preservative compositions of this invention may include antifungaland/or termiticidal components in addition to those discussed above,singly or in combinations. Examples include without limitation tungstateand/or molybdate ions as described in U.S. Provisional Application No.60/755,213; tropolones as described in U.S. Provisional Application No.60/755,242; and hydrolyzed olefin/maleic anhydride copolymers asdescribed in U.S. Provisional Application No. 60/755,211; each of theabove provisional applications being incorporated in its entirety as apart hereof for all purposes.

Molybdate and/or tungstate ions used as additional components inpreservative solutions of this invention may be obtained from anysoluble source of molybdate or tungstate, such as potassium molybdate,ammonium molybdate, sodium molybdate dihydrate, molybdenum oxide,molybdic acid, potassium tungstate, ammonium tungstate, sodium tungstatedihydrate, tungsten oxide, tungstic acid. Additional compounds that maybe used as sources of tungstate or molybdate ions include compounds suchas silicotungstates, phosphotungstates, borotungstates,silicomolybdates, phosphomolybdates and boromolybdates.

Molybdate and/or tungstate ions form complexes with copper and/or zincions that are insoluble in water, but that have substantial if notcomplete solubility in a solvent system such as an ammoniacal solution.These components penetrate a cellulosic material such as wood whendissolved in solution, and are retained in the wood after loss of theammonia. When molybdate and/or tungstate ions are used as additionalpreservative components in a composition having complexes of copperand/or zinc, copper and/or zinc is added in sufficient amount to formcomplexes with both the ibuprofen component and the molybdate and/ortungstate component. Suitable amounts of molybdate and/or tungstate ionsrange from about 10 to about 6,000 ppm depending on factors related tothe use to be made of the cellulosic material, as discussed above.Particularly suitable is a concentration between about 200 and about1,700 ppm.

The term “tropolone” is commonly used to refer to tropolone itself(2-hydroxycyclohepta-2,4,6-trienone) and compounds that are derivativesof tropolone and have similar properties, such as the natural compoundsbeta-thujaplicin (also known as hinokitiol), gamma-thujaplicin, andbeta-dolabrin. Any of these tropolones having antifungal and/ortermiticidal activity may be used as additional components in thepreservative compositions of this invention. These compounds are solublein methanol and ethanol but relatively insoluble in water.

Tropolones also form complexes with copper and/or zinc ions that areinsoluble in water but that have substantial if not complete solubilityin a solvent system such as an ammoniacal solution. This componentpenetrates a cellulosic material such as wood when dissolved insolution, and is retained in the wood after loss of a solvent such asammonia. When a tropolone is used as an additional preservativecomponent in a composition containing copper and/or zinc ions, copperand/or zinc is added in an amount sufficient to form a complex with boththe ibuprofen component and the tropolone component. Suitable amounts oftropolone for use in a composition hereof range from about 100 to about1,000 ppm depending on factors related to the use to be made of thecellulosic material, as discussed above. Particularly suitable is aconcentration between about 200 and about 700 ppm.

Hydrolyzed olefin/maleic anhydride copolymers form complexes with copperand/or zinc ions that are insoluble in water, but that have substantialif not complete solubility in a solvent system such as an ammoniacalsolution. This component penetrates a cellulosic material such as woodwhen dissolved in solution, and is retained in the wood after loss of asolvent such as ammonia. When hydrolyzed olefin/maleic anhydridecopolymers are an additional preservative component in a compositioncontaining copper and/or zinc ions, copper and/or zinc ions are added inan amount sufficient to form a complex with both the ibuprofen componentand the hydrolyzed olefin/maleic anhydride copolymer component.

Hydrolyzed olefin/maleic anhydride copolymers are prepared by hydrolysisof olefin/maleic anhydride copolymers, using for example aqueous NaOH,to form negatively charged carboxylate anions which can complex withcopper and zinc ions. Olefins of particular use in the olefin/maleicanhydride copolymers for hydrolysis are octene and styrene. Mixtures ofdifferent types of olefin/maleic anhydride copolymers, such as a mixtureof octene/maleic anhydride copolymer and styrene/maleic anhydridecopolymer may also be used. The synthesis of olefin/maleic anhydridecopolymers is known from sources such as U.S. Pat. No. 3,706,704 andU.S. Pat. No. 3,404,135, and copolymers suitable for use herein aregenerally between about 10,000 and about 50,000 in molecular weight.

A preferred process for the synthesis of styrene/maleic anhydridecopolymers, which results in copolymers of molecular weight rangingbetween 20,000 and 100,000, depending on the specific conditions used,makes use of a combination of toluene and isopropyl alcohol as both asolvent and as a chain transfer agent. Using this combination, ratherthan isopropyl alcohol alone, reduces the percent of mono isopropylmaleate ester formed during the polymerization from about 20% to about1%. In addition, the molecular weight of the copolymer product isincreased from about 18,000 when using isopropyl alcohol alone, to over20,000 when using a toluene:isopropanol ratio of 1:1. Molecular weightsof over 90,000 may be achieved using a ratio of 76:4.

Copolymers of up to about 1,000,000 molecular weight may be used in thepreservative compositions of the invention, but, in concentratedsolution, copolymers with greater than about 80,000 molecular weight areviscous and therefore difficult to use. Therefore, preferred in thisinvention are olefin/maleic anhydride copolymers with molecular weightbelow about 80,000. More preferred are copolymers with molecular weightsranging between 2,000 and about 40,000.

In addition, a copper chelating compound, such as is described in U.S.Pat. No. 6,978,724 (which is incorporated in its entirety as a parthereof for all purposes), may be included in a composition hereof toenhance copper retention in treated articles. A suitable copperchelating compound may have a functional group such as one r more of thefollowing: amidoximes, hydroxamic acids, thiohydroxamic acids,N-hydroxyureas, N-hydroxycarbamates, and N-nitroso-alkyl-hydroxylamines.A suitable copper chelating compound forms a complex with copper and/orzinc that is insoluble in water, but has solubility in an ammoniacalsolution that is similar to the solubility of the ibuprofen--copperand/or zinc complex described above. The complex formed by the chelatingcompound also penetrates a cellulosic material deeply when dissolved inthe solution, and is retained in the wood after loss of a solvent orco-solvent such as ammonia. When a copper chelating compound is presentas an additional component in a composition of this invention, copperand/or zinc ions are added in sufficient amount such that it/they formcomplexes with both the ibuprofen and the chelating compound.

A functional group in a copper chelating compound can be provided bymethods such as the following: in an amidoxime, reactingnitrile-containing compounds with hydroxylamine; in a hydroxamic acid,adding hydroxylamine to anhydride groups of copolymers such asstyrene/maleic anhydride or octene/maleic anhydride, and formingstyrene/N-hydroxymaleamic acid copolymer or octene/N-hydroxymaleamicacid copolymer; in a thiohydroxmic acid, adding hydroxylalmine todithiocarboxylic acids; in a N-hydroxyurea, reacting hydroxylamine withan isocyanate; in a N-hydroxycarbamate, by reacting hydroxylamine witheither a linear or cyclic carbonate; and in aN-nitroso-alkyl-hydroxylamine, by nitrosation of alkyl hydroxylamines.

Preferred chelating compounds contain two or more amidoxime and/orhydroxamic acid groups. By acid catalysis, the amidoxime functionalitycan be readily converted to the corresponding hydroxamic acidfunctionality in aqueous solution. A convenient route to this preferredclass of compounds is by addition of hydroxylamine to the correspondingnitrile compound. Various methods are known for preparing nitrilecompounds. A particularly useful method is cyanoethylation, in whichacrylonitrile, or other unsaturated nitrile, undergoes a conjugateaddition reaction with protic nucleophiles such as alcohols and amines.Preferred amines for cyanoethylation are primary amines, secondaryamines having 1 to 30 carbon atoms, and polyethylene amine. Preferably,a cyanoethylation catalyst is used, such as lithium hydroxide, sodiumhydroxide, or potassium hydroxide, between about 0.05 mol % and 15 mol %based on unsaturated nitrile.

A wide variety of materials can be cyanoethylated. Cyanoethylates can bederived from the reaction of acrylonitrile with carbohydrates, such asregenerated cellulose, dextran, dextrin, gums (guar, locust bean, honeylocust, flame tree, tara, arabic, tragacanth, and karaya); starches(corn, potato, tapioca and wheat); or modified natural polymers such ascellulose xanthate, dimethylthiourethane of cellulose, ethyl cellulose,ethylthiourethane of cellulose, hydroxyethylcellulose, methylcellulose,and phenylthiourethane of cellulose. Other natural polymers that havebeen cyanoethylated include flax, jute, manila, sisal, and proteins suchas blood albumin, casein, gelatin, gluten, soybean protein, wool, cornzein, or materials derived from such natural polymers. Pre-treatment ofhigh molecular weight or water-insoluble carbohydrates and starches withenzymes may be used if necessary to increase the solubility of theamidoxime or hydroxamic acid copper complex in an aqueous ammonia,ethanolamine or pyridine solution.

Synthetic polymers such as acetone-formaldehyde condensate,acetone-isobutyraldehyde condensate, methyl ethyl ketone-formaldehydecondensate, poly(allyl alcohol), poly(crotyl alcohol),poly(3-chloroallyl alcohol), ethylene-carbon monoxide copolymers,polyketone from propylene, ethylene and carbon monoxide, poly(methallylalcohol, poly(methyl vinyl ketone, and poly(vinyl alcohol) have alsobeen cyanoethylated and can also serve as platforms for furthermodification into metal-binding polymers.

Preferably the cyanoethylates are derived from sucrose and sorbitol.Most preferred is cyanoethylated sorbitol (DS=6.0), called CE-Sorb6.

The nitrile groups of these cyanoethylates or cyanoalkylates can bereacted with hydroxylamine to form the amidoxime or hydroxamic acid. Ifhydroxylamine hydrochloride is used instead of hydroxylamine, sodiumhydroxide, sodium carbonate or ammonium hydroxide may be used toneutralize the hydrochloric acid. Ammonium hydroxide is preferred. Theamidoxime of sorbitol can be prepared by hydroxylamine reaction ofCE-Sorb6. This amidoxime of sorbitol is particularly useful as anadditional component in the preservative compositions of this invention.

Preservative Treatment A solution of ibuprofen and copper and/or zinccomplexes, optionally containing additional preservative compounds, maybe applied by dipping, brushing, spraying, soaking, draw-coating,rolling, pressure-treating or other known methods. The preservativecompositions may be applied to any cellulosic material, including forexample wood, lumber, plywood, oriented strand board, cellulose,hemicellulose, lignin, cotton and paper. Particularly efficacious isimbibing into wood under the standard pressure treatment process forwaterborne preservative systems. A vacuum may be applied before and/orafter application of the wood preservative. Removal of air from the woodunder vacuum, then breaking the vacuum in the presence of preservativesolution, enhances penetration of the solution into the wood.

A particularly useful treatment process for wood is as follows: Wood,either dry or fresh cut and green is placed in a chamber that is thensealed and evacuated in a regulated cycle which is determined by thespecies of wood. Generally, for Southern Yellow Pine (SYP) wood, theperiod of evacuation is about 30 minutes, during which time the pressurewithin the sealed chamber is brought to a level of about two inches ofmercury or less. The evacuated pressure in the chamber can vary from0.01 to 0.5 atm. The purpose of this step is to remove air, water, andvolatiles from the wood. The preservative compositions of the inventionthen are introduced into the closed chamber in an amount sufficient toimmerse the wood completely without breaking the vacuum to the air.Pressurization of the vessel is then initiated and the pressuremaintained at a desired level by a diaphragm or other pump for a givenperiod of time. Initially, the pressure within the vessel will decreaseas the aqueous composition within the container penetrates into thewood. The pressure can be raised to maintain a desirable levelthroughout the penetration period of treatment. Stabilization of thepressure within the vessel is an indication that there is no furtherpenetration of the liquid into the wood. At this point, the pressure canbe released, the wood allowed to equilibrate with the solution atatmospheric pressure, the vessel drained, and the wood removed. In thispart of the process, the pressures used can be as high as 300 psig, andare generally from about 50 to 250 psig.

Articles Incorporating Preservative Compositions

Articles of this invention are those having been treated with apreservative composition described herein. Following treatment ofarticles such as those made from or incorporating wood, lumber, plywood,oriented strand board, paper, cellulose, cotton, lignin, andhemicellulose, the ammonia in an ammoniacal solution of the preservativecomposition will dissipate. The ibuprofen—copper and/or zinc complex isretained on and/or in the article. Additional components, if included inthe composition used for treatment, are retained on and/or in thetreated articles as well.

Compositions containing components in addition to an ibuprofen-copperand/or zinc complex that are particularly suitable for treatment of anarticle include those that contain hydrolyzed olefin/maleic anhydridecopolymers; copper chelating compounds having at least two functionalgroups selected from amidoximes, hydroxamic acids, thiohydroxamic acids,N-hydroxyureas, N-hydroxycarbamates, and N-nitroso-alkyl-hydroxylamines;molybdate and/or tungstate ions; or a tropolone; and mixtures of thesecomponents. Particularly useful in such compositions is a copperchelating compound with at least two hydroxamic groups being derivedfrom styrene/maleic anhydride or octene/maleic anhydride, or a copperchelating compound based on an amidoxime of sorbitol.

The process of this invention for treating cellulosic material alsoincludes a step of incorporating the cellulosic material, or a treatedarticle containing the cellulosic material, such as wood, into astructure such as a house, cabin, shed, burial vault or container, ormarine facility, or into a consumable device such as a piece of outdoorfurniture, or a truss, wall panel, pier, sill, or piece of decking for abuilding.

EXAMPLES

The present invention is further illustrated in the following Examples.It should be understood that these Examples are given by way ofillustration only. From the above discussion and these Examples, oneskilled in the art can ascertain the essential characteristics of thisinvention, and without departing from the spirit and scope thereof, canmake various changes and modifications of the invention to adapt it tovarious usages and conditions.

The meaning of abbreviations is as follows: “conc.” means concentrated,“sec” means second(s), “ml” means milliliter(s), “L” means liter(s), “g”means gram(s), “mmol” means millimole(s), “mtorr” means millitorr(s),“hr” means hour(s), “min” means minute(s), “mm” means millimeter(s),“cm” means centimeter(s), “nm” means nanometer(s), “Mw” means weightaverage molecular weight, “Mn” means number average molecular weight,“mw” means molecular weight, “XRF” stands for X-ray fluorescencespectroscopy, “RH” is relative humidity, “MHz” means megahertz, “NMR”means nuclear magnetic resonance, “IR” means infrared, “ICP” means ioncouples plasma, “LC/MS means liquid chromatography/mass spectroscopy,and “S/S” means stainless steel. “SD” is standard deviation, “SMA” isstyrene/maleic anhydride copolymer, “SMA-NOH” isstyrene/N-hydroxymaleamic acid copolymer, “OMA” is octene/maleicanhydride copolymer. “SYP” is “southern yellow pine”, an acronym forclosely related pine species that includes Pinus caribaea Morelet, Pinuselliottii Englelm., Pinus palustris P. Mill., Pinus rigida P. Mill., andPinus taeda L. “AWPA” is the American Wood-Preserver's Association. AWPAstandards are published in the “AWPA Book of Standards”, AWPA P.O. Box5690, Granbury, Tex. 76049. The protocol for preservation of SYP stakesis based on AWPA Standard, Method E7-01, Sec. 4, 5, 6, and 7 and E11-97.According to AWPA Standard E7-01, the stakes are graded visuallyaccording to the following criterion for fungal decay and insect attackas follows:

Decay Grades Grade No. Description of Condition 10 Sound. 9.5 Suspicionof decay permitted 9 Trace decay to 3% of cross section 8 Decay from 3to 10% of cross section 7 Decay from 10 to 30% of cross section 6 Decayfrom 30 to 50% of cross section 4 Decay from 50 to 75% of cross section0 Failure

Termite Grades Grade No. Description of Condition 10 Sound. 9.5 1 to 2small nibbles permitted 9 Slight evidence of feeding to 3% of crosssection 8 Attack from 3 to 10% of cross section 7 Attack from 10 to 30%of cross section 6 Attack from 30 to 50% of cross section 4 Attack from50 to 75% of cross section 0 Failure

The termite grades and decay grades are used to report insect damage andwood decay, respectively, in the tables below. “Gross retention” refersto the amount of treatment liquid remaining in the wood immediatelyafter imbibition. “Retention” refers to the amount of preservativeremaining in the wood after the imbibing liquid has been removed fromthe wood by drying. The amount can be expressed as ppm or as a weight. A“witness stake” or “witness sample” is a whole stake, or a portion of atreated stake, that will be retained as a sample for future analysis.“DS” is degree of substitution.

General Methods

All reactions and manipulations were carried out in a standardlaboratory fume hood open to atmosphere. Deionized water was used wherewater is called for in the subsequent procedures. Sorbitol, AIBN,acrylonitrile, lithium hydroxide monohydrate, hydroxylaminehydrochloride, copper sulfate pentahydrate, and Chromazurol S[1667-99-8] were obtained from Sigma-Aldrich Chemical (Milwaukee, Wis.)and used as received. Concentrated ammonium hydroxide and glacial aceticacid were obtained from EM Science (Gibbstown, N.J.) and used asreceived. Cyanoethylated sucrose [18307-13-7] and copper acetatemonohydrate were obtained from Acros Organics (Geel, Belgium) and usedas received. Sucrose was obtained from Pathmark Supermarket (Wilmington,Del.) and used as received. pH was determined with pHydrion paper fromMicro Essential Laboratory (Brooklyn, N.Y.). Degree of substitution (DS)of the cyanoethylate is expressed in terms of equivalents ofacrylonitrile used in the cyanoethylation step. IR spectra were recordedusing a Nicolet Magna 460 spectrometer. LC/MS analyses were performedusing a Micromass LCT instrument. NMR spectra were obtained on a BrukerDRX Avance (500 MHz ¹H, 125 MHz ¹³C) using deuterated solvents obtainedfrom Cambridge Isotope Laboratories. Elemental analyses were performedby Micro-Analytical Inc, Wilmington, Del. Pressure treatment of southernyellow pine wood was performed in a high-pressure lab using stainlesssteel pressure vessels following the AWPA standard process (AWPA P5-01).XRF analysis was performed on an Axios Wavelength Dispersive X-rayFluorescence Spectrometer manufactured by Panalytical Inc., Eindhoven,Netherlands.

Chromazurol S Test for Presence of Copper

Treated wood was tested for the presence of copper with Chromazurol Susing the method described by AWPA A3-00 Sec. 2. A 0.167% w/wChromazurol S in 1.67% w/w aqueous sodium acetate solution was sprayedonto a freshly cut treated wood surface. A change from the yellowsolution color to a dark blue color in the sprayed area indicates that aminimum of 25 ppm copper is present. Stakes 965 mm (38″) long are cut to457 mm (18″) from each end and the remaining 50.8 mm (2″) piece (witnesspiece) in the middle was treated on the freshly cut surface with thespray solution of Chromazurol-S. A freshly cut surface turned dark blueon exposure to the solution, which is an indication of completepenetration of the wood by the wood preservative treatment solution.

Dimensions of Wood as per AWPA E17-01 Sec. 4.2.4:

All wood was cut using inch measurements. The wood was cut as accuratelyas practicable, given that wood will change dimensions with moisturecontent; the cutting error is estimated to be within one mm in anydimension. Conversions to metric are provided.

-   Fahlstrom stake: 0.156″×1.5″×10″(4 mm×38 mm×254 mm)-   Decay stake: ¾″×¾″×18″(19 mm×19 mm×450 mm)-   Pre-Decay stakes: ¾″×¾″×38″(19 mm×19 mm×1154 mm)-   Depletion stake: 1.5″×1.5″×18″(38 mm×38 mm×450 mm)-   Blocks: ¾″×¾″×¾″(19 mm×19 mm×19 mm)    Preparation of Styrene/Maleic Anhydride Copolymer

Styrene/maleic anhydride copolymer (SMA) was prepared as described inco-pending application with US filing #60/855211, which is hereinincorporated by reference, as follows.

An 18 L multi-necked flask was equipped with two dropping funnels,reflux condenser, heating mantel, mechanical stirrer, and nitrogenbubbler. The flask was charged with 9500 g (11 L) of toluene and 500 g(640 ml) of isopropanol. To this solution was added 1276 g of maleicanhydride powder. A solution of 15 g of AIBN dissolved in 500 g (578 ml)of toluene was prepared and placed in one of the dropping funnels. Thesecond funnel was charged with 1302.6 g of styrene. The apparatus wassealed and purged with nitrogen. The maleic anhydride solution waswarmed to 60° C. and about one-third of the AIBN solution was added.Then about 150 ml of styrene was added to the flask from the funnel.There was about a 5 minute induction period during which oxygen wasconsumed. After a white precipitate began to form, indicating that thepolymerization had begun, the remaining styrene was added in 150 mlportions during 60 minutes. The AIBN solution was added in thirds over60 minutes. The addition of styrene and AIBN maintained the reactiontemperature at about 70° C. to 80° C. without much additional heat fromthe mantel. After addition was complete, the reaction temperature wasmaintained at about 80° C. for an additional 2 hours by using theheating mantel. The white slurry of copolymer was then cooled to aboutroom temperature, filtered, washed with warm toluene, and dried in avacuum oven at 90° C. to obtain 2460 g (95.5% yield) of SMA and 40 g ofmono isopropyl maleate. The Mw =40,400 and the Mn=18,600. The washingswere evaporated to give an additional 0.4 g of mono isopropyl maleate(¹H NMR (CDCl₃): δ1.32 (d, J =1.2, CH3, 6H) , 5.15 (m, CH, 1H), 6.36 (m,CH, 2H) ppm.

Preparation of Hydrolyzed Octene/Maleic Anhydride Copolymer

A 1:1 co-polymer of octene and maleic anhydride monosodium salt wasprepared as described in U.S. Pat. Nos. 3706704 and 3404135. The Mw ofthe octane/maleic anhydride copolymer (OMA), which is the precursor ofhydrolyzed 1:1 octene/maleic anhydride copolymer monosodium salt, wasdetermined by size exclusion chromatography to be 8595+/−50. Theresulting co-polymer was hydrolyzed with aqueous sodium hydroxidesolution and brought to a 27.1% w/w solution in water.

Preparation of CE-Sorb6: Cyanoethylation of Sorbitol

A 1000 ml 3-necked round-bottomed flask equipped with an mechanicalstirrer, reflux condenser, nitrogen purge, dropping funnel, andthermometer was charged with water (18.5 ml) and lithium hydroxidemonohydrate (1.75 g) and the first portion of sorbitol (44.8 g). Thesolution was heated to 42° C. with a water bath with stirring and thesecond portion of sorbitol (39.2 g) was added directly to the reactionflask. The first portion of acrylonitrile (100 ml) was then added to thereaction drop-wise via a 500 ml addition funnel over a period of 2 hr.The reaction was slightly exothermic, raising the temperature to 51° C.The final portion of sorbitol (32 g) was added for a total of 0.638moles followed by a final portion of acrylonitrile (190 ml) over 2.5 hrwhile keeping the reaction temperature below 60° C. (A total of 4.41moles of acrylonitrile was used.) The reaction solution was then heatedto 50-55° C. for 4 hr. The solution was then allowed to cool to roomtemperature and the reaction was neutralized by addition of acetic acid(2.5 ml). Removal of the solvent under reduced pressure gave the productas a clear, viscous oil (324 g). The IR spectrum showed a peak at 2251cm⁻¹, indicative of the nitrile group. A DS=5.6 was determined by LC/MS,which is rounded to 6 in CE-Sorb6.

Reaction of CE-Sorb6 with Hydroxylamine Hydrochloride

A 1000 ml three-necked round-bottomed flask was equipped with amechanical stirrer, condenser, and addition funnel under nitrogen.CE-Sorb6 (14.77 g, 29.5 mmol) and water (200 ml) were added to the flaskand stirred. In a separate 500 mL Erlenmeyer flask, hydroxylaminehydrochloride (11.47 g, 165 mmol, 5.6 eq) was dissolved in water (178ml) and then treated with ammonium hydroxide (22.1 ml of 28% ammoniasolution, 177 mmol, 6.0 eq) for a total volume of 200 ml. Thehydroxylamine solution was then added in one portion directly to themixture in the round-bottomed flask at room temperature. The stirredmixture was heated at 80° C. for 2 hr, pH=8-9, and then allowed to coolto room temperature. The IR spectrum indicated loss of most of thenitrile peak at 2250 cm⁻¹ and the appearance of a new peak at 1660 cm⁻¹,indicative of the amidoxime or hydroxamic acid.

EXAMPLE 1 Ammoniacal Solution of Styrene/N-Hydroxymaleamic AcidCopolymer, Ibuprofen/Copper Complex, and Molybdate/Copper Complex asPreservative

A) Preparation of Styrene/N-Hydroxymaleamic Acid Copolymer,Ibuprofen/Copper Complex, and Molybdate/Copper Complex in AmmoniacalSolution

A 5 L round-bottomed flask equipped with addition funnel, heatingmantel, thermocouple well, and mechanical stirrer was charged with 72.2g (0.357 mol) of styrene/maleic anhydride copolymer (SMA) resin(prepared as described in General Methods) and 500 ml of water. Asolution of 23.6 g of hydroxylamine 50% w/w in water (0.357 mol) and18.9 g sodium carbonate (0.179 mol) in 101 ml of water was added throughthe addition funnel during 15 minutes. The mixture was heated for 3hours at 55° C. to give a clear solution containingstyrene/N-hydroxymaleamic acid copolymer. To the polymer solution wasadded 250 g of conc. ammonium hydroxide, 250 ml of water, 11.1 of sodiumibuprofen (Aldrich, Milwaukee, Wis.), 15.14 g of sodium molybdatedihydrate, and 116.7 g (0.468 mol) of copper sulfate pentahydrate. Theproduct was diluted with water to a final weight of 20 Kg to give animbibing solution containing 1485 ppm copper, 500 ppm of ibuprofen, and500 ppm of molybdate ion.

B) Wood preservation treatment procedure and Environmental Testing forDecay Stakes Treated with Ammoniacal Solution of Ibuprofen/CopperComplex, Molybdate/Copper Complex, and Styrene/N-Hydroxymaleamic AcidCopolymer

Selection and Preparation of Stakes

The following methods are based on AWPA Standard, Method E7-01, Sec. 4,5, 6, and 7 and E11-97.

SYP boards, 3.175 cm×35.56 cm×243.84 cm ( 5/4″×14″×8 ft) and 3.175cm×30.48 cm×243.84 cm ( 5/4″×12″×8 ft) were obtained from DelawareCounty Supply (Boothwin, Pa.). The boards were cut into pre-decay stakesof 19 mm×19 mm×96.5 cm (¾″×¾″×38″) in size (AWPA Standard, Method E7-01,Sec 4.2, with the exception that the boards were milled withoutequilibration). The stakes were segregated by visual inspection (AWPAStandard, Method E7-01, Sec. 4.1) and stakes having knots, cracks, resinand sap pockets, signs of infection by mold, stain, and wood destroyingfungi were eliminated. The remaining stakes were sorted into groups byweight (AWPA Standard, Method E7-01, Sec. 5). The group of stakesweighing between 200 g and 220 g was chosen for the imbibing experimentand placed in a controlled environment chamber at 23° C. and RH of 50%(Model 1-60LLVL Humidity Cabinet, Percival Scientific Inc., Boone, Iowa)for 21 days (AWPA Standard, Method E7-01, Sec. 4 and E11-97, Sec. 3).After equilibration in the environment chamber, each stake was equippedwith two S/S identification tags and secured with 24.6 mm S/S nails.Each stake was then weighed (weights given in Table 1: Dry weight) anddimensioned and the results recorded.

Wood Preservation Treatment Procedure

Treatment was carried out in a stainless steel pressure vessel designedand fabricated at the DuPont Experimental Station (Wilmington, Del.).Pressure was supplied by a Diaphragm Pump (Model S216J10; SpragueProducts Div. of Curtiss-Wright Flow Control Corp., Brecksville, Ohio).The pressure vessel was constructed from sched. 80 SS pipe measuring12.7 cm (5″) diam. and was closed at each end with SS flanges and caps.The length of the pipe varied depending on the length of the wood to betreated. Typically, a 101.6 cm (40″) length was chosen for treating 38″wood specimens. Other lengths of pipe were added via flanges to extendthe length of the pressure vessel to accommodate 243.84 cm (8 ft)specimens or shorter lengths of pipe were used to treat 25.4 cm (10″)specimens.

Ten labeled pre-decay stakes were loaded into a stainless steelseparation rack (to simulate sticking, which is physical separation oflumber by placing small pieces of wood between boards to separate them),as well as two witness stakes (total 12 stakes), and placed in thepressure vessel. The pressure vessel was sealed and a vacuum of 69.85 cmHg gauge (13.5 psig) was applied for a period of 30 minutes. The vacuumwas broken by introduction of the imbibing fluid (the solution preparedin Example 1A) to fill the pressure vessel and cover the wood. Airpockets were removed by circulating imbibing fluid through the vessel,and pressure of 7.18 kilopascal gauge (150 psig) was applied with adiaphragm pump for a period of 30 minutes. The pressure was released andthe stakes allowed to equilibrate in the imbibing solution for 15minutes. The pressure vessel was drained and the treatment rack bearingthe stakes was removed. The stakes were lightly wiped with a papertowel, weighed (weights given in Table 1: Wet weight), and placed onopen racks in a ventilated enclosure to dry. The original dry weightsubtracted from the wet weight for each block indicated the amount ofuptake of treatment solution, as given in Table 1.

TABLE 1 Penetration of Treatment Solution in SYP Pre- Decay Stakes GrossStake Dry wt Wet wt retention Dry Wt. 3 wks ID (g) (g) (g) (g) F1767211.06 458.16 247.1 212.37 F1769 209.26 466.97 257.71 210.6 F1771 203.37454.77 251.4 205.59 F1773 193.25 431.84 238.59 194.5 F1775 206.12 452.81246.69 207.33 F1777 207.03 455.74 248.71 209.87 F1779 203.81 442.08238.27 204.9 F1781 192.99 450.63 257.64 194.78 F1783 202.01 454.16252.15 203.31 F1785 207.96 454.46 246.5 209.78

After 14 days the stakes were weighed, the results recorded, andreturned to the humidity chamber. After a total of 21 days in thechamber, the stakes were weighed and the results recorded in Table 1column5 (AWPA Standard, Method E7-01, Sec. 6).

Two additional sets of stakes, prepared as described above, wereseparately imbibed with 1:2 and 1:4 dilutions of the solution preparedin Example 1A. Dilutions were made with a 1.4% ammonia water solution.In addition, a set of stakes was prepared and imbibed with a 1.4%ammonia water solution to serve as controls.

The four sets of 10 labeled stakes were cut to 45.7 cm (18″) decay stakelength, cutting from each end and leaving a 5.1 cm (2″) witness sectionfrom the center of the stake. All witness sections were tested forcopper penetration using the Chromazurol S test described in the GeneralMethods. All witness sections tested turned dark blue indicatingcomplete penetration of the wood by the wood preservative treatmentsolution.

Each 45.7 cm (18″) stake was weighed, dimensioned and the resultsrecorded. The groups of 10 stakes from each half were bundled togetherand labeled for ground insertion at two separate test sites (Newark,Del. and Starke, Fla.). The bundles were stored in a cool area (AWPAStandard, Method E7-01, Sec. 7) until the stakes were installed in theground. The stakes were placed in the ground as per AWPA E7-01. Thepositioning of the stakes was randomized in the test sites as per AWPAE7-01. At 12 months the stakes in Starke, Fla. were removed from theground and visually graded for decay and termite attack (insect damage)according to AWPA protocol E7-01. Results are given in Table 2, alongwith the average of gradings for a set of stakes with the same treatmentsolution, and the standard deviation. A score of 10 indicates no decayor damage. A score of 0 indicates complete decomposition.

TABLE 2 Decay and insect damage data for stakes treated with differentdilutions of styrene/N- hydroxymaleamic acid copolymer, ibuprofen/coppercomplex, and molybdate/copper complex and tested in Starke, FL. 12 mograding Insect Treatment Stake ID Decay damage 00189 F1768 10 10 1485ppm Cu/500 ppm MoO₄/ F1770 10 10 500 ppm Ibuprofen/SMA-NOH F1772 10 10F1774 10 10 F1776 10 10 F1778 9 8 F1780 MD MD F1782 10 10 F1784 10 10F1786 10 10 Avg 9.9 9.8 SD 0.31 0.63 00190 F1838 10 10 743 ppm Cu/250ppm MoO₄/250 ppm F1840 9 10 Ibuprofen/SMA-NOH F1842 8 10 F1844 10 10F1846 10 10 F1848 10 10 F1850 10 10 F1852 9 10 F1854 7 10 F1856 10 10Avg 9.3 10 SD 1.01 0 00191 F1858 10 10 371 ppm Cu/125 ppm MoO₄/125 ppmF1860 10 10 Ibuprofen/ F1862 8 8 SMA-NOH F1864 10 10 F1866 10 9 F1868 98 F1870 10 10 F1872 10 10 F1874 7 7 F1876 7 8 Avg 9.1 9 SD 1.22 1.1000195 F1988 10 10 Solvent Control Water/Ammonia F1990 7 7 F1992 8 10F1994 9 10 F1996 9 10 F1998 10 10 F2000 9 10 W0402 10 10 W0404 10 10W0406 10 9 Avg 9.2 9.6 SD 0.98 0.92 MD = mechanical damage

At 12 months the stakes in Newark, Del. were removed from the ground andgraded. A summary of the results are given in Table 3 as averages of thegradings, along with averages of the gradings at Starke from Table 2.

TABLE 3 Averages of decay and insect damage scores for stakes treatedwith different dilutions of styrene/N- hydroxymaleamic acid copolymer,ibuprofen/copper complex, and molybdate/copper complex and tested inNewark, DE and Starke, FL. Avg insect Location Treatment Time (Months)Avg Decay damage Starke, FL 1485 ppm Cu/500 ppm MoO₄/500 ppm 12 9.9 9.8Ibupofen/SMA-NOH 743 ppm Cu/250 ppm MoO₄/250 ppm 12 9.3 10Ibupofen/SMA-NOH 371 ppm Cu/125 ppm MoO₄/125 ppm 12 9.1 9Ibupofen/SMA-NOH Control 12 9.2 9.6 Newark, 1485 ppm Cu/500 ppm MoO₄/500ppm 12 10 10 DE Ibupofen/SMA-NOH 743 ppm Cu/250 ppm MoO₄/250 ppm 12 1010 Ibupofen/SMA-NOH 371 ppm Cu/125 ppm MoO₄/125 ppm 12 10 10Ibupofen/SMA-NOH Control 12 9.7 10

Since there was little decay and insect damage at these sites in 12months, the differences between the treated and control stakes are smallto none. It is expected that over longer periods of time, treated stakeswill show less decay and insect damage with respect to controls at thesesites.

EXAMPLE 2 Ammoniacal solution of Ibuprofen, Styrene/N-HydroxymaleamicAcid Copolymer and Copper/Tungstate Complex as Preservative

A) Preparation of Ibuprofen, Styrene/N-Hydroxymaleamic Acid Copolymerand Copper/Tungstate Complex in Ammoniacal solution

A 5 L round-bottomed flask equipped with addition funnel, heatingmantel, thermocouple well, and mechanical stirrer was charged with 81.7g (0.404 mol) of SMA resin (prepared as described in General Methods)and 500 ml of water. A solution of 26.7 g of hydroxylamine 50% w/w inwater (0.404 mol) and 21.4 g sodium carbonate (0.202 mol) in 102 ml ofwater was added through the addition funnel during 15 minutes. Themixture was heated for 3 hours at 55° C. to give a clear solution. Tothe polymer solution was added 200 g of conc. ammonium hydroxide, 100 mlof water, 11.1 of sodium ibuprofen, 13.3 g of sodium tungstatedihydrate, and 116.7 g (0.468 mol) of copper sulfate pentahydrate. Theproduct was diluted with water to a final weight of 20 Kg to give animbibing solution containing 1485 ppm copper, 500 ppm of ibuprofen, and500 ppm of tungstate ion.

B) Penetration of Ammoniacal Solution of Ibuprofen,Styrene/N-Hydroxymaleamic Acid Copolymer and Copper/Tungstate Complex inWood Blocks

The ammoniacal solution of ibuprofen, styrene/N-hydroxymaleamic acidcopolymer and copper/tungstate complex prepared in Example 2A wasimbibed into wood using a wood impregnation system similar to thatdescribed by the American Wood Preservers Association (AWPA) as AWPAStandard, Method E11-97. Standard laboratory glassware and a vacuum pumpwere used to imbibe 32 pre-weighed Southern Yellow Pine (SYP) woodblocks measuring 19 mm×19 mm×19 mm. The blocks were free of knots, resinand sap pockets, had no visible sign of infection by mold, stain, andwood destroying fungi, had no cracks, had a ring count of 6-10 rings perinch, and contained at least 50% summer wood. The blocks werepre-conditioned for 21 days in a humidity chamber set at 23° C.+/−0.50°C. and relative humidity of 50%+/−2%. Under these conditions the blocksachieved equilibrium moisture content of 9-10%, which was determined byusing a Moisture Meter, Model PM6304 from the Control Company(Friendswood, Tex.). The blocks were weighed, and weights recorded inTable 2 (dry weight). An imbibing vessel was prepared using a glassflask measuring 10.16 cm in diam.×30.48 cm long having three openings,two of which were standard taper ground glass 29/26 joints and a centralone having a standard taper ground glass 102/75 ball joint. An additionfunnel was placed on one of the 29/26 joints and filled with thetreatment solution. The wood cubes were placed in the imbibing vessel ina Nylon bag that was weighted with stainless steel nuts to preventfloating and the imbibing vessel was evacuated for 30 min. The vacuumwas broken by introduction of 800 ml of imbibing solution. This amountof solution was sufficient to cover the blocks. Thirty-two blocks wereimbibed with the ibuprofen, styrene/N-hydroxymaleamic acid copolymer andcopper/tungstate_complex ammoniacal solution prepared in Example 2A. Theblocks were imbibed under atmospheric pressure for 30 minutes. Theblocks were gently wiped with a towel to remove any surface solution andwere then immediately weighed while wet to ensure that the wood waspenetrated by the imbibing solution. Table 4 shows that the blocksgained weight and that the imbibing was successful.

TABLE 4 Solution Penetration in wood blocks treated with ammoniacalsolution of ibuprofen, styrene/N- hydroxymaleamic acid copolymer andcopper/tungstate complex. Gross dry wt wet wt Retention ID# (g) (g) (g)E2000111.00164B1 3.7651 8.7851 5.0200 E2000111.00164B2 3.7762 8.82885.0526 E2000111.00164B3 3.7989 8.8683 5.0694 E2000111.00164B4 3.70248.9358 5.2334 E2000111.00164B5 3.7495 8.7519 5.0024 E2000111.00164B63.7336 8.8576 5.1240 * E2000111.00164B7 3.7509 8.882 5.1311E2000111.00164B8 3.7654 8.7191 4.9537 E2000111.00164B9 3.6952 8.89415.1989 * E2000111.00164B10 3.7696 8.8722 5.1026 E2000111.00164B11 3.73838.8606 5.1223 * E2000111.00164B12 3.7243 8.8693 5.1450 *E2000111.00164B13 3.6304 8.4484 4.8180 E2000111.00164B14 3.6986 8.61084.9122 E2000111.00164B15 3.7361 7.3361 3.6000 E2000111.00164B16 3.71748.8297 5.1123 * E2000111.00164B17 3.7336 8.7432 5.0096 E2000111.00164B183.7096 8.8448 5.1352 E2000111.00164B19 3.7725 8.9467 5.1742E2000111.00164B20 3.7318 8.7683 5.0365 E2000111.00164B21 3.7797 8.91815.1384 E2000111.00164B22 3.6461 8.8339 5.1878 E2000111.00164B23 3.68158.8583 5.1768 E2000111.00164B24 3.6839 8.7593 5.0754 E2000111.00164B253.7436 8.7211 4.9775 E2000111.00164B26 3.6802 8.8776 5.1974E2000111.00164B27 3.7695 8.7463 4.9768 E2000111.00164B28 3.6679 8.94465.2767 E2000111.00164B29 3.6875 8.8085 5.1210 E2000111.00164B30 3.71898.9465 5.2276 * E2000111.00164B31 3.6554 8.5079 4.8525 E2000111.00164B323.6937 8.8544 5.1607 119.107 161.3220 *marks blocks having a grossretention falling within +/− 5% of the group average

Decay stakes were prepared as per Example 1 using the solution preparedin Example 2A. In addition, a 1:2 dilution of the solution prepared inExample 2A, and a 1:4 dilution of the solution prepared in Example 2Awere used to treat decay stakes in the same manner. The same controlstakes as in Example 1, Table 2 were used for comparison. The stakeswere placed in the ground in Starke, Fla. and examined after 12 monthsfor decay and insect damage as per AWPA standard E7-01. The results aregiven in Table 5.

TABLE 5 Decay and insect damage data for stakes treated with differentdilutions of ammoniacal solution of ibuprofen, styrene/N-hydroxymaleamicacid copolymer and copper/tungstate complex and tested in Starke, FL. 12mo grading Insect Treatment Stake ID decay damage 1485 ppm Cu/500 ppmWO₄/500 ppm F1546 10 10 Ibuprofen/SMA-NOH F1548 8 10 F1550 10 10 F155210 10 F1554 10 10 F1556 10 10 F1558 10 10 F1562 10 10 F1564 7 7 F1566 1010 Avg 9.50 9.70 SD 1.03 0.90 743 ppm Cu/250 ppm WO₄/250 ppm F1618 10 10Ibuprofen/SMA-NOH F1620 10 10 F1622 10 10 F1624 10 10 F1626 7 7 F1628 1010 F1630 10 10 F1632 10 10 F1634 10 10 F1636 10 10 Avg 9.70 9.70 SD 0.900.90 321 ppm Cu/125 ppm WO₄/125 ppm F1638 10 10 Ibuprofen/SMA-NOH F164010 10 F1642 10 10 F1644 10 10 F1646 6 6 F1648 10 10 F1650 10 10 F1652 1010 F1654 9 10 F1656 9 8 Avg 9.40 9.40 SD 1.20 1.28 00195 F1988 10 10Solvent Control Water/Ammonia F1990 7 7 F1992 8 10 F1994 9 10 F1996 9 10F1998 10 10 F2000 9 10 W0402 10 10 W0404 10 10 W0406 10 9 Avg 9.20 9.6SD 0.98 .92

In a similar manner, Decay Stakes were prepared with the same treatmentand environmentally tested in Newark, Del. A summary of the results aregiven in Table 6 as averages of gradings at Newark, and Starke (fromTable 5).

TABLE 6 Averages of decay and insect damage data for stakes treated withdifferent dilutions of ammoniacal solution of ibuprofen,styrene/N-hydroxymaleamic acid copolymer and copper/tungstate complexand tested in Newark, DE, compared to Starke, FL results. Avg InsectLocation Treatments: Conc. in ppm Time (Months) Avg Decay damage Starke,FL Cu 1485/WO₄ 500/Ibupofen 500/SMA-NOH 12 9.5 9.7 Cu 743/WO₄250/Ibupofen 250/SMA-NOH 12 9.7 9.7 Cu 371/WO₄ 125/Ibupofen 125/SMA-NOH12 9.4 9.4 Control 12 9.2 9.6 Newark, Cu 1485/WO₄ 500/Ibupofen500/SMA-NOH 12 10 10 DE Cu 743/WO₄ 250/Ibupofen 250/SMA-NOH 12 10 10 Cu371/WO₄ 125/Ibupofen 125/SMA-NOH 12 10 10 Control 12 9.7 10

Since there was little decay and insect damage at these sites in 12months, the differences between the treated and control stakes is smallto none. It is expected that over longer periods of time, treated stakeswill show less decay and insect damage with respect to controls at thesesites.

EXAMPLE 3 Ammoniacal Solution of Ibuprofen, Hydrolyzed Octene/MaleicAnhydride Copolymer and Copper/Tungstate Complex as Preservative

A) Preparation of Ibuprofen, Hydrolyzed Octene/Maleic AnhydrideCopolymer and Copper/Tungstate Complex in Ammoniacal Solution

A 2 L resin kettle was charged with 6.64 of sodium ibuprofen, 8.00 g ofsodium tungstate dihydrate, 300 g of water and 250 g of conc. ammoniumhydroxide. To this solution was added 116.7 g of copper sulfatepentahydrate. To this was added 382.5 g of a 27.1% aqueous solution ofhydrolyzed copolymer of octene/maleic anhydride monosodium salt,prepared as described in General Methods. The mixture was diluted with1.4% ammonium hydroxide to give a final weight of 20 Kg. The finalsolution contained 1485 ppm of copper, 300 ppm of tungstate ion, and 300ppm of ibuprofen.

B) Wood Preservation Treatment Procedure and Environmental Testing forPre-Decay Stakes Treated with Ammoniacal Solution of Ibuprofen,Hydrolyzed Octene/Maleic Anhydride Copolymer and Copper/TungstateComplex

Ten pre-decay stakes were prepared and treated with the solutionprepared in Example 3A as described in Example 1B. The uptake (GrossRetention) of treatment solution is evident from the results given inTable 7.

TABLE 7 Retention of Treatment Solution in SYP Pre-Decay Stakes GrossDry Wt Wet Wt Retention ID (g) (g) (g) W1167 216.84 463.07 246.23 W1169230.06 446.52 216.46 W1171 218.87 455.22 236.35 W1173 216.94 455.33238.39 W1175 215.46 450.57 235.11 W1177 227.32 466.27 238.95 W1179214.75 448.95 234.2 W1181 216.68 463.57 246.89 W1183 212.97 452.77 239.8W1185 219.58 447.6 228.02

The 10 labeled stakes were cut to 45.7 cm (18″) lengths, cutting fromeach end and leaving a 5.1 cm (2″) witness section from the center ofthe stake. All witness sections were tested for copper penetration usingthe Chromazurol S test described in the General Methods. All witnesssections tested turned dark blue indicating complete penetration of thewood by the wood preservative treatment solution.

Each 45.7 cm (18″) stake was weighed, dimensioned and the resultsrecorded. The group of 10 stakes from each half were bundled togetherand labeled for ground insertion at two separate test sites (Newark,Del. and Starke, Fla.). The bundles were stored in a cool area (AWPAStandard, Method E7-01, Sec. 7) until the stakes were installed in theground. The stakes were placed in the ground as per AWPA E7-01. Thepositioning of the stakes was randomized in the test sites as per AWPAE7-01. After 12 months the stakes in Starke, Fla. were removed from theground and visually graded for decay and termite attack (insect damage)according to AWPA protocol E7-01. The results are given in Table 8.

TABLE 8 Decay and insect damage data for stakes treated with ammoniacalsolution of ibuprofen, hydrolyzed octene/maleic anhydride copolymer andcopper/tungstate complex and tested in Starke, FL. 12 mo grading InsectTreatment stake ID decay damage 1485 ppm Copper/300 ppm 1168 10 10WO₄/300 ppm Ibuprofen/ 1170 10 10 hydrolyed OMA 1172 10 10 1174 10 91176 10 10 1178 10 10 1180 10 10 1182 10 10 1184 10 10 1186 10 10 Avg 109.9 SD 0 0.3 Untreated Controls 1440 0 0 1442 8 6 1444 0 0 1446 6 6 14486 6 1450 6 4 1452 6 6 1454 6 4 1456 0 0 1458 6 6 Avg 4.40 3.80 SD 2.942.60

Stakes treated with the test solution showed much less damage thanuntreated control stakes. The stakes in Newark, Del. were graded at 12months. A summary of the results are given in Table 9 as averages ofgradings at the Newark site, in comparison to the averages at the Starkesite (from Table 8).

TABLE 9 Averages of decay and insect damage data for stakes treated withammoniacal solution of ibuprofen, hydrolyzed octene/maleic anhydridecopolymer and copper/tungstate complex and tested in Newark, DE,compared with Starke, FL results. Avg. Time Avg Insect LocationTreatment: Conc. In ppm (Months) Decay damage Starke, FL Cu 1485/WO₄300/Ibuprofen 12 10 9.9 300/hydrolyzed OMA Cu 743/WO₄ 150/Ibuprofen 129.65 9.8 150/hydrolyzed OMA Cu 371/WO₄ 75/Ibuprofen 12 9.35 9.3575/hydrolyzed OMA Control 12 4.4 3.8 Newark, Cu 1485/WO₄ 300/Ibuprofen12 10 10 DE 300/hydrolyzed OMA Cu 743/WO₄ 150/Ibuprofen 12 9.95 10150/hydrolyzed OMA Cu 371/WO₄ 75/Ibuprofen 12 9.85 9.9 75/hydrolyzed OMAControl 12 8.8 9.75

With damage to controls extensive, strong protection by all treatmentsolutions was observed at the Starke, Fla. site. Since there was littledecay and insect damage at the Newark site in 12 months, the differencesbetween the treated and control stakes are small. It is expected thatover longer periods of time, treated stakes will show less decay andinsect damage with respect to controls at this site.

EXAMPLE 4 Ammoniacal Solution of Ibuprofen/Copper/Tungstate Complex andCE-Sorb6 amidoxime as Preservative

A) Preparation of Ibuprofen/Copper/Tungstate Complex and CE-Sorb6

A solution of 116.7 g of copper sulfate pentahydrate, 7.98 g of sodiumtungstate dihydrate, 6.64 g of sodium ibuprofen, 155 g of conc. ammoniumhydroxide (57% ammonium hydroxide), and 250 g of water was prepared. Tothis was added 92.2 g of a 57% solution of the amidoxime of CE-Sorb6having a DS=6.0 (prepared as described in General Methods). The mixturewas stirred for 30 minutes at room temperature to prepare a concentratedwood preservation solution. The concentrated solution was then dilutedto a final weight of 20 Kg with 1.4% aqueous ammonium hydroxide solutionto prepare a wood preservation solution having 1485 ppm copper, 300 ppmibuprofen, and 300 ppm tungstate ion.

B) Wood Preservation Treatment Procedure and Environmental Testing forPre-Decay Stakes Treated with Ammoniacal Solution ofIbuprofen/Copper/Tungstate Complex and CE-Sorb6 amidoxime

Ten stakes were prepared and treated with the solution prepared inExample 4A as described in Example 1B. The uptake of treatment solutionwas evident from the results given in Table 10.

TABLE 10 Penetration of Treatment Solution in SYP Pre-decay Stakes GrossDry Wt Wet Wt Retention ID (g) (g) (g) W2119 233.29 450.13 216.84 W2121245.66 470.04 224.38 W2123 245.64 468.11 222.47 W2125 246.77 484.46237.69 W2127 240.22 470.31 230.09 W2129 239.22 471.75 232.53 W2131239.87 476.4 236.53 W2133 426.15 471.89 45.74 W2135 232.6 474.7 242.1W2137 249.8 483.59 233.79

The 10 labeled stakes were cut to 45.7 cm (18″) decay stake length,cutting from each end and leaving a 5.1 cm (2″) witness section from thecenter of the stake. All witness sections were tested for copperpenetration using the Chromazurol S test described in the GeneralMethods. All witness sections tested turned dark blue indicatingcomplete penetration of the wood by the wood preservative treatmentsolution.

Pre-decay stakes were similarly prepared and treated with 1:2 and 1:4dilutions of the treatment solution prepared in Example 4A. Each 45.7 cm(18″) stake was weighed, dimensioned and the results recorded. The groupof 10 stakes from each half were bundled together and labeled for groundinsertion at two separate test sites (Newark, Del. and Starke, Fla.).The bundles were stored in a cool area (AWPA Standard, Method E7-01,Sec. 7) until the stakes were installed in the ground. The stakes wereplaced in the ground as per AWPA E7-01. The positioning of the stakeswas randomized in the test sites as per AWPA E7-01. After 12 months, thestakes in Starke, Fla. were removed from the ground and visually gradedfor decay and termite attack according to AWPA protocol E7-01. Stakestreated with ammoniacal solution of ibuprofen/copper/tungstate complexand CE-Sorb6 amidoxime prepared in Example 4A show less damage thancontrols as seen in the results in Table 11.

TABLE 11 Decay and insect damage data for Decay stakes treated withdifferent dilutions of ammoniacal solution of ibuprofen/copper/tungstatecomplex and CE-Sorb6 amidoxime tested in Starke, FL. 12 mo scores InsectTreatment Stake ID Decay damage Copper(1485 ppm)/WO4(300 ppm/ 1168 10 10Ibuprofen(300 ppm)/CE-Sorb6 1170 10 10 amidoxime 1172 10 10 1174 10 91176 10 10 1178 10 10 1180 10 10 1182 10 10 1184 10 10 1186 10 10 Avg 109.9 SD 0 0.3 Copper(742 ppm)/WO4(150 ppm)/ 1258 10 10 Ibuprofen(150ppm)/CE-Sorb6 1260 10 10 amidoxime 1262 9.5 10 1264 10 10 1266 8 8 126810 10 1270 10 10 1272 10 10 1274 10 10 1276 9 10 Avg 9.65 9.8 SD 0.630.6 Copper(371 ppm)/WO4(75 ppm)/ 1278 10 10 Ibuprofen(75 ppm)/CE-Sorb61280 9 10 amidoxime 1282 10 10 1284 9.5 9 1286 8 7 1288 10 10 1290 8 101292 9 10 1294 10 8 1296 10 9.5 Avg 9.35 9.35 SD 0.78 1.00 UntreatedControls 1440 0 0 1442 8 6 1444 0 0 1446 6 6 1448 6 6 1450 6 4 1452 6 61454 6 4 1456 0 0 1458 6 6 Avg 4.4 3.8 SD 2.94 2.6

The stakes in Newark, Del. were also graded at 12 months. A summary ofthe results are given in Table 12 as averages of gradings, compared tothe averages for the Starke site.

TABLE 12 Averages of decay and insect damage data for Decay stakestreated with different dilutions of ammoniacal solution ofibuprofen/copper/tungstate complex and CE-Sorb6 amidoxime tested inNewark, De and Starke, FL. Avg Time Avg Insect Location Treatment: Conc.in ppm (Months) Decay damage Starke, FL Cu 1485/WO₄ 300/ 12 10 9.9Ibuprofen 300/CE-Sorb6 amidoxime Cu 743/WO₄ 150/ 12 9.65 9.8 Ibuprofen150/CE-Sorb6 amidoxime Cu 371/WO₄ 75/ 12 9.35 9.35 Ibuprofen 75/CE-Sorb6amidoxime Control 12 4.4 3.8 Newark, Cu 1485/WO₄ 300/Ibuprofen 12 10 9.9DE 300/CE-Sorb6 amidoxime Cu 743/WO₄ 150/ 12 10 9.95 Ibuprofen150/CE-Sorb6 amidoxime Cu 371/WO₄ 75/Ibuprofen 12 9.8 9.95 75/CE-Sorb6amidoxime Control 12 8.8 9.75

With decay and insect damage to controls extensive, strong protection byall treatment solutions was observed at the Starke, Fla. site. Sincethere was little decay and insect damage at the Newark site in 12months, the differences between the treated and control stakes aresmall. It is expected that over longer periods of time, treated stakeswill show less decay and insect damage with respect to controls at thissite.

Preparation and Environmental Testing of Fahlstrom Stakes Treated withAmmoniacal solution of Ibuprofen/Copper/Tungstate Complex and CE-Sorb6Selection and preparation of Fahlstrom stakes

The following methods are based on AWPA Standard, Method E7-01, Sec. 4,5, 6, and 7 and E11-97.

SYP boards, 3.175 cm×35.56 cm×243.84 cm ( 5/4″×14″×8 ft) and 3.175cm×30.48 cm×243.84 cm ( 5/4″×12″×8 ft) were obtained from DelawareCounty Supply (Boothwin, Pa.). The boards were cut into Fahlstrom stakesof 4 mm×38 mm×254 cm (0.156″×1.5″×10″) in size (AWPA Standard, MethodE7-01, Sec 4.2, with the exception that the boards were milled withoutequilibration). The stakes were segregated by visual inspection (AWPAStandard, Method E7-01, Sec. 4.1) and stakes having knots, cracks, resinand sap pockets, signs of infection by mold, stain, and wood destroyingfungi were eliminated. The remaining stakes were sorted into groups byweight (AWPA Standard, Method E7-01, Sec. 5). Stakes weighing between 20g and 25 g were chosen for the imbibing experiment and placed in acontrolled environment chamber at 23° C. and RH of 50% (Model 1-60LLVLHumidity Cabinet, Percival Scientific Inc., Boone, Iowa) for 21 days(AWPA Standard, Method E7-01, Sec. 4 and E11-97, Sec. 3). Afterequilibration in the environment chamber, each stake was identified by apainted number. Each stake was then weighed and dimensioned and theresults recorded.

Treatment of the Fahlstrom stakes was carried out in a stainless steelpressure vessel designed and fabricated at the DuPont ExperimentalStation (Wilmington, Del.). Pressure was supplied by a Diaphragm Pump(Model S216J10; Sprague Products Div. of Curtiss-Wright Flow ControlCorp., Brecksville, Ohio). The pressure vessel was constructed fromsched. 80 SS pipe measuring 12.7 cm (5″) diam. and was closed at eachend with SS flanges and caps. The length of the pipe varied depending onthe length of the wood to be treated. Typically, a 101.6 cm (40″) lengthwas chosen for treating 38″wood specimens. Other lengths of pipe wereadded via flanges to extend the length of the pressure vessel toaccommodate 243.84 cm (8 ft) specimens or shorter lengths of pipe wereused to treat 25.4 cm (10″) specimens.

Batches of ten labeled stakes were loaded into a stainless steelseparation rack (to simulate sticking, which is physical separation oflumber by placing small pieces of wood between boards to separate them,as well as two witness stakes (total 12 stakes), and placed in thepressure vessel. The pressure vessel was sealed and a vacuum of 69.85 cmHg gauge (13.5 psig) was applied for a period of 30 minutes. The vacuumwas broken by introduction of the imbibing fluid, the ammoniacalsolution of ibuprofen/copper/tungstate complex and CE-Sorb6 prepared inExample 4A, to fill the pressure vessel and cover the wood. Air pocketswere removed by circulating imbibing fluid through the vessel, andpressure of 7.18 kilopascal gauge (150 psig) was applied with adiaphragm pump for a period of 30 minutes. The pressure was released andthe stakes allowed to equilibrate in the imbibing solution for 15minutes. The pressure vessel was drained and the treatment rack bearingthe stakes was removed. The stakes were lightly wiped with a paper toweland weighed. The Fahlstrom stakes gained weight in a manner similar tothe stakes in Tables 1. and 3., which indicated that the ammoniacalsolution of ibuprofen/copper/tungstate complex and CE-Sorb6 wassuccessfully imbibed into the wood. Fahlstrom stakes were similarlytreated with 1:2 and 1:4 dilutions of the treatment solution prepared inExample 4A.

The Fahlstrom stakes described were placed in the ground, along withuntreated control stakes, at Hialeah, Fla., Starke, Fla., Newark, Del.,and LaPlace, La. as per AWPA E7-01. The positioning of the stakes wasrandomized in the test sites as per AWPA E7-01. The stakes wereevaluated for decay at 6 months vs. untreated control stakes accordingto AWPA standard E7-01. Results from the stakes in Hialeah are given inTable 13.

TABLE 13 Decay gradings of Fahlstrom stakes treated with ammoniacalsolution of ibuprofen/copper/tungstate complex and CE-Sorb6 amidoxime atHialeah, FL. Aug. 1, 2006 Installed Feb. 2, 2006 6 mo Treatment Stake IDdecay 1485 ppm Copper/300 ppm WO₄/300 ppm 261-02 10 Ibuprofen/CE-Sorb6amidoxime 261-03 10 261-06 10 261-09 10 261-13 10 261-28 10 261-30 10261-38 10 261-41 10 261-42 10 Avg 10 SD 0 Copper (742 ppm)/WO₄ (150ppm)/ 263-05 10 Ibuprofen (150 ppm)/CE-Sorb6 amidoxime 263-06 10 263-149.5 263-15 10 263-18 9 263-20 10 263-26 10 263-37 9 263-38 10 263-43 10Avg 9.75 SD 0.40 Copper (371 ppm)/WO₄ (75 ppm)/ 264-05 9 Ibuprofen (75ppm)/CE-Sorb6 amidoxime 264-11 8 264-17 7 264-23 10 264-24 8 264-27 9.5264-28 10 264-35 10 264-39 10 264-44 10 Avg 9.15 SD 1.05 UntreatedControls 275-01 8 275-04 7 275-05 7 275-07 6 275-08 8 275-11 6 275-13 7275-15 6 275-18 8 275-20 8 Avg 7.1 SD 0.83

A summary of the results for 6 month gradings of the stakes at all foursites is given in Table 14 as averages of gradings at each site.

TABLE 14 Averages of decay and insect damage scores for Fahlstrom stakestreated with ammoniacal solution of ibuprofen/copper/tungstate complexand CE-Sorb6 amidoxime Time Avg Insect Location Treatment:: Conc. in ppm(Months) Avg Decay damage Starke, FL Cu 1485/WO₄ 300/Ibuprofen 300/ 68.9 9.9 CE-Sorb6 amidoxime Cu 743/WO₄ 150/Ibuprofen 150/ 6 7.7 10CE-Sorb6 Cu 371/WO₄ 75/Ibuprofen 75/CE- 6 8.9 10 Sorb6 amidoxime Control6 9.2 9.2 Newark, DE Cu 1485/WO₄ 300/Ibuprofen 300/ 6 10 10 CE-Sorb6amidoxime Cu 743/WO₄ 150/Ibuprofen 150/ 6 10 10 CE-Sorb6 Cu 371/WO₄75/Ibuprofen 75/CE- 6 10 10 Sorb6 amidoxime Control 6 7.9 9.3 Hialeah,Cu 1485/WO₄ 300/Ibuprofen 300/ 6 10 xxxx FL CE-Sorb6 amidoxime Cu743/WO₄ 150/Ibuprofen 150/ 6 9.75 xxxx CE-Sorb6 amidoxime Cu 371/WO₄75/Ibuprofen 75/CE- 6 9.15 xxxx Sorb6 amidoxime Control 6 7.1 xxxxLaPlace, Cu 1485/WO₄ 300/Ibuprofen 300/ 7 9.9 10 LA CE-Sorb6 amidoximeCu 743/WO₄ 150/Ibuprofen 150/ 7 9.7 10 CE-Sorb6 amidoxime Cu 371/WO₄75/Ibuprofen 75/CE- 7 9.2 10 Sorb6 amidoxime Control 7 8.9 9.9 xxxxmeans no insect damage observed at this site

Protection from decay was observed for all treatments at the Hialeahsite. It is expected that over longer periods of time, treated Fahlstromstakes will show less decay and insect damage with respect to controlsat the additional testing sites

1. An aqueous composition comprising in admixture (a) a complex comprising (i) ibuprofen, and (ii) copper ions, zinc ions or a mixture thereof; and (b) ammonia and/or ethanolamine; wherein component (b) is present in an amount sufficient to solubilize the complex.
 2. The composition of claim 1 which further comprises a component (c) selected from one or both of an additional antifungal component and an additional termiticidal component.
 3. The composition of claim 2 wherein the component (c) comprises molybdate ions, tungstate ions, a tropolone, or mixtures thereof.
 4. The composition of claim 1 further comprising at least one hydrolyzed olefin/maleic anhydride copolymer.
 5. The composition of claim 4 wherein the copolymer is hydrolyzed octene/maleic anhydride copolymer, hydrolyzed styrene/maleic anhydride copolymer, or mixtures thereof.
 6. The composition of claim 1 further comprising a copper chelating compound comprising at least two functional groups selected from the group consisting of amidoxime, hydroxamic acid, thiohydroxamic acid, N-hydroxyurea, N-hydroxycarbamate, and N-nitroso-alkyl-hydroxylamine.
 7. The composition of claim 6 wherein the chelating compound comprises at least two hydroxamic groups and the chelating compound is derived from styrene/maleic anhydride or octene/maleic anhydride.
 8. The composition of claim 6 wherein the chelating compound comprises at least two functional groups selected from amidoxime and hydroxamic acid, and the amidoxime or hydroxamic acid is derived from a cyanoethylated compound.
 9. The composition of claim 8 wherein the cyanoethylated compound is derived from the cyanoethylation of a primary amine, a secondary amine, blood albumin, casein, soybean protein, wool, or corn zein; or from materials derived from blood albumin, casein, gelatin, gluten, soybean protein, wool, or corn zein.
 10. The composition of claim 8 wherein the cyanoethylated compound is derived from the cyanoethylation of synthetic polymers selected from the group consisting of acetone-formaldehyde condensate, acetone-isobutyraldehyde condensate, methyl ethyl ketone-formaldehyde condensate, poly(allyl alcohol), poly(crotyl alcohol), poly(3-chloroallyl alcohol), ethylene carbon monoxide copolymers, polyketone from propylene, ethylene and carbon monoxide, poly(methallyl alcohol), poly(methyl vinyl ketone), and poly(vinyl alcohol).
 11. The composition of claim 8 wherein the cyanoethylated compound is obtained from the cyanoethylation of materials selected from the group of: alcohols, carbohydrates, dextran, dextrin, gums, starches, modified natural polymers; and compounds derived from natural polymers.
 12. The composition of claim 8 wherein the cyanoethylated compound is obtained from the cyanoethylation of sucrose or sorbitol.
 13. A process for preserving cellulosic material, or an article that comprises cellulosic material, comprising contacting the cellulosic material or article with the composition of claim
 1. 14. The process of claim 13 wherein the cellulosic material is selected from the group consisting of wood, lumber, plywood, oriented strand board, cellulose, hemicellulose, lignin, cotton and paper.
 15. The process of claim 13 which comprises dipping, brushing, spraying, draw-coating, rolling, or pressure-treating the cellulosic material or article with the composition of claim
 1. 16. The process of claim 13 wherein the cellulosic material is wood or lumber.
 17. The process of claim 16 further comprising subjecting the wood or lumber to a vacuum before and/or after it is contacted with the composition of claim
 1. 18. The process of claim 13 further comprising a step of incorporating the cellulosic material or the article into a structure or into a consumable device.
 19. Cellulosic material, or an article comprising a cellulosic material, wherein the composition of claim 1 is adsorbed on and/or absorbed in the cellulosic material.
 20. The material or article of claim 19 wherein the cellulosic material is selected from the group consisting of wood, paper, cellulose, cotton, lignin, and hemicellulose.
 21. The material or article of claim 19 wherein the cellulosic material is selected from the group consisting of wood, lumber, plywood, oriented strand board, paper, cellulose, cotton, lignin and hemicellulose; and the composition further comprises an ibuprofen—copper and/or zinc ion complex.
 22. The material or article of claim 19 wherein the composition further comprises a tungstate and/or molybdate ion—copper and/or zinc ion complex.
 23. The material or article of claim 19 wherein the composition further comprises a hydrolyzed olefin/maleic anhydride copolymer.
 24. The material or article of claim 19 wherein the composition further comprises a copper chelating compound comprising at least two functional groups selected from the group consisting of amidoxime, hydroxamic acid, thiohydroxamic acid, N-hydroxyurea, N-hydroxycarbamate, and N-nitroso-alkyl-hydroxylamine.
 25. The material or article of claim 24 wherein the chelating compound comprises at least two hydroxamic groups and is derived from styrene/maleic anhydride or octene/maleic anhydride.
 26. The material or article of claim 24 wherein the chelating compound comprises at least two functional groups selected from amidoxime and hydroxamic acid, and the amidoxime or hydroxamic acid is derived from a cyanoethylated compound.
 27. The material or article of claim 26 wherein the cyanoethylated compound is obtained from the cyanoethylation of sucrose or sorbitol.
 28. A structure or consumable device comprising the cellulosic material or article of claim
 19. 